CN101678564A - Polymer composite material, apparatus for producing the same and method of producing the same - Google Patents

Polymer composite material, apparatus for producing the same and method of producing the same Download PDF

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Publication number
CN101678564A
CN101678564A CN200880014294A CN200880014294A CN101678564A CN 101678564 A CN101678564 A CN 101678564A CN 200880014294 A CN200880014294 A CN 200880014294A CN 200880014294 A CN200880014294 A CN 200880014294A CN 101678564 A CN101678564 A CN 101678564A
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China
Prior art keywords
mentioned
living beings
mixing
polymer composite
thing
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Pending
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CN200880014294A
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Chinese (zh)
Inventor
大野孝
白石信夫
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Joetsu Agriculture Future Co Ltd
AGRI FUTURE JOETSU CO Ltd
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Joetsu Agriculture Future Co Ltd
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Priority claimed from JP2007263880A external-priority patent/JP4638903B2/en
Priority claimed from JP2007263879A external-priority patent/JP4660528B2/en
Application filed by Joetsu Agriculture Future Co Ltd filed Critical Joetsu Agriculture Future Co Ltd
Publication of CN101678564A publication Critical patent/CN101678564A/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/84—Venting or degassing ; Removing liquids, e.g. by evaporating components
    • B29B7/845—Venting, degassing or removing evaporated components in devices with rotary stirrers
    • B29B7/847—Removing of gaseous components before or after mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B29B7/484—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws with two shafts provided with screws, e.g. one screw being shorter than the other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/84—Venting or degassing ; Removing liquids, e.g. by evaporating components
    • B29B7/842—Removing liquids in liquid form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/84—Venting or degassing ; Removing liquids, e.g. by evaporating components
    • B29B7/845—Venting, degassing or removing evaporated components in devices with rotary stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29B7/86—Component parts, details or accessories; Auxiliary operations for working at sub- or superatmospheric pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/397—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using a single screw
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/57—Screws provided with kneading disc-like elements, e.g. with oval-shaped elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/76—Venting, drying means; Degassing means
    • B29C48/765—Venting, drying means; Degassing means in the extruder apparatus
    • B29C48/766—Venting, drying means; Degassing means in the extruder apparatus in screw extruders
    • B29C48/767—Venting, drying means; Degassing means in the extruder apparatus in screw extruders through a degassing opening of a barrel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/06—Rod-shaped
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

It is intended to provide a technique for making a biomass-origin dispersion phase of a polymer composite material, wherein the dispersion phase is formed in a synthetic polymer matrix, highly microscopic and homogeneous. An apparatus (10) for producing a polymer composite material characterized by comprising: a cylinder (13) in which a supply area (A) for supplying the main component of the synthetic polymer as described above and an excessive water-containing component originating in a biomass as described above is provided in the upstream side while a discharge unit (17) is provided in thedownstream side; a screw (15) which axially rotates within the cylinder (13), which has been set to a kneading temperature (Tz) at which the synthetic polymer melts, and extrudes the kneaded matter comprising the main component and the excessive water-containing matter as described above toward the discharge unit (17); and a dehydration unit (40) by which the water contained in the kneaded matteris removed under setting pressures (Pa, Pb, Pc) being lower than the saturated vapor pressure (Pz) at the kneading temperature (Tz) employed in the cylinder (13) but higher than atmospheric pressure.

Description

Polymer composite, its manufacturing installation and manufacture method thereof
Technical field
The invention belongs to and the relevant technical field of polymer composite that mixes by synthetic high polymer and living beings origin composition, particularly relate to manufacturing installation and the manufacture method thereof of making such polymer composite.
Background technology
At this, so-called living beings (living resources) are meant capable of regeneration organic property resource in the animal or plant of the energy growth that utilizes the sun.
Specifically, can list lignocellulosic or be that the vegetation matter of main component is living beings (as the thinnings of the discarded object of timber industry and pulp industry etc., building disintegration material etc., straw, beanpod shell, rice husk etc. as agricultural wastes), is that the starchiness of main component is living beings (rice, wheat, corn, potato, sweet potato, tapiocas etc.) with amylose or amylopectin that the chitin (or shitosan) that derives from shellfish is living beings (crab shell, shrimp shells etc.) with the cellulose.
Now; carrying out following research: by making composition and compoundization of synthetic high polymer that derives from these living beings, creation is sent as an envoy to by the use amount minimizing of the synthetic high polymer of fossil resource production and to preserving our planet that environment contributes or showing the polymer composite of unexistent new function in the past.For such polymer composite, how that living beings origin composition is fine and be distributed to equably in the parent phase of synthetic high polymer and become important research project.
But living beings have the high crystalline based on intermolecular firm hydrogen bond, and have higher structures such as three-dimensional cross-linked.Even under the situation of mechanical crushing, the powder of living beings also has the character of easy gathering.Therefore, be not easy to make living beings origin composition fine and be distributed to equably in the parent phase of synthetic high polymer usually.
As prior art at above-mentioned problem, known have a following technology: in living beings is that above-mentioned starchiness is when being living beings, after it has been carried out aqueous treatment, host with synthetic high polymer adds hot milling, thereby make starch gelatinization (αization), and make it fine and be distributed to (for example patent documentation 1) in the parent phase equably.
And, be that vegetation matter is living beings or chitin when being living beings in living beings, known have a following technology: adopt high-pressure homogenizer etc. with the miniaturization and make the suspension of homogeneous in aqueous solvent of these living beings.Then, this suspension is added hot milling with the host of synthetic high polymer, thus living beings origin composition is fine and be distributed to (for example patent documentation 2) in the parent phase equably.
Patent documentation 1: TOHKEMY 2006-21502 communique
Patent documentation 2: TOHKEMY 2006-289164 communique
Summary of the invention
The problem that invention will solve
But in above-mentioned prior art, there are the following problems: in mixing processing procedure, fine and dispersed equably living beings origin composition can't be avoided the phenomenon that partly reassociates in the open dehydration procedure that carries out sharp because of atmospheric pressure.Therefore, not enough by the decentralized photo of the polymer composite of above-mentioned prior art manufacturing with respect to the degree of reaching of the miniaturization of parent phase, homogenising.
The present invention is a problem to address the above problem, and purpose is to provide a kind of technology of making polymer composite, and described polymer composite is that the miniaturization of decentralized photo height, the homogenising of the living beings origin composition in the parent phase of synthetic high polymer are formed.
The scheme that is used to deal with problems
In order to solve above-mentioned problem, the present invention is a kind of manufacturing installation of making polymer composite, this polymer composite is that synthetic high polymer and living beings origin composition mix, the manufacturing installation of this polymer composite is characterised in that, it comprises: mixing parts, and the mixing thing to the superfluous moisture thing that contains above-mentioned living beings origin composition at least under the melting temperature that is set carries out mixing; Dehydration part is forcing down than the saturated vapor under the above-mentioned melting temperature and, under the high setting pressure the mixing thing that contains above-mentioned host and the moisture thing of above-mentioned surplus is being dewatered than atmospheric pressure; Take out parts, it is used to take out the above-mentioned mixing thing that has dewatered.
The effect of invention
According to the present invention, provide the decentralized photo height miniaturization of the living beings origin composition in the parent phase that a kind of manufacturing makes synthetic high polymer, the technology of polymer composite that homogenising forms.
Description of drawings
(a) of Fig. 1 is the longitudinal section along rotating shaft of the 1st embodiment of the manufacturing installation of expression polymer composite of the present invention, (b) being the partial sectional view that amplifies the part of its dehydration part of expression, (c) is the state diagram of water that is used to illustrate the function of this dehydration part.
(a) of Fig. 2 is the longitudinal section along rotating shaft of the 2nd embodiment of the manufacturing installation of expression polymer composite of the present invention, (b) is the longitudinal section along rotating shaft of expression the 3rd embodiment.
(a)～(c) of Fig. 3 is manufacturing installation and longitudinal section rotating shaft direct cross of the polymer composite of expression the 4th embodiment.
Description of reference numerals
10,10 ', 10 ", 60 manufacturing installations
12 hoppers (input parts)
13 cylinder bodies
14 inlets
15,15 ', 15 " screw rod
16 steps (flight)
17 take out parts
20 pressing parts
30 force decompressor
40 (40a, 40b, 40c, 40d, 40e) dehydration part
41 filters
42 isolated walls
45 voltage regulation parts
50,62 mixing parts
63 housings
65 rotors
67 take out parts
61,68 open and close parts
The A raw material drops into interval
The mixing interval of B
C1 pressurizing and dehydrating interval (between drying zone)
Between C2 normal pressure drying zone (between drying zone)
C3 decompression dehydration interval (between drying zone)
D is again between pressor areas
The P0 atmospheric pressure
Saturated vapour pressure under the Pz melting temperature
Px (Pa, Pb, Pc, Pd, Pe) setting pressure
The Tz melting temperature
The V gasification space
The mixing space of W (enclosure space)
The specific embodiment
With reference to the accompanying drawings embodiments of the present invention are described.
The 1st embodiment
(a) of Fig. 1 is the longitudinal section of the 1st embodiment of the manufacturing installation 10 (being designated hereinafter simply as " manufacturing installation ") of expression polymer composite of the present invention.
This manufacturing installation 10 contains and drops into parts 12 (hopper), mixing parts 50, dehydration part 40, forces decompressor 30 and constitute.At this, mixing parts 50 are the structures that contain driver part 11, cylinder body 13, screw rod 15.
By such formation manufacturing installation 10, when the raw material of polymer composite are dropped into by input parts 12, these raw material are by mixing around the screw rod 15 that axis rotates in the inside of cylinder body 13, and carry out processed by dehydration part 40 and pressure decompressor 30, will become the molten mass taking-up of polymer composite from taking out parts 17.
In addition, the molten mass of this polymer composite is pencil and is emitted by being set at the punch die (omitting diagram) that takes out on the parts 17 and offer tens place's apertures.And, after solidifying by the cooling duct, be introduced in the comminutor (omitting diagram) and be cut into the particle of grain of rice shape.
Driver part 11 is connected with an end of screw rod 15, is used to make this screw rod 15 to rotate around axis, is the power source that the raw material of polymer composite are mixing.In addition, 15 expressions of screw rod are one in Fig. 1, but manufacturing installation 10 is not limited to the manufacturing installation of such single shaft, also comprise two above screw rods 15 manufacturing installation of the multiaxis of formation side by side.
Like this, in the manufacturing installation 10 that is made of multiaxis, driver part 11 makes set a plurality of screw rods 15 rotate around axis respectively.In addition, in this case, the direction and the speed of rotating around axis separately of a plurality of screw rods 15 are any item of setting.
Dropping into parts 12 is used for and will puts into the inside of cylinder body 13 as the superfluous moisture thing of the host of the raw-material synthetic high polymer of polymer composite and living beings origin composition.The component of the material that this is dropped into and fit rate can at random be set by supply unit 12a, the 12b of the superfluous moisture thing of supplying with synthetic high polymer and living beings origin composition respectively.
In addition, derive under the situation that starchiness is living beings at living beings origin composition, on these input parts 12, be provided with the water filling parts sometimes, these water filling parts are used to inject the such as described later needed moisture of gelatinization of this living beings origin composition, thereby make this living beings origin become to be divided into superfluous moisture thing.
At this, be put to the material in the manufacturing installation 10 as synthetic high polymer, can adopt the thermoplastic resin of fusion or any one in the cured thermosetting by heating by heating.
As the material that can be used as the host of thermal plastic high polymer, be preferably shaped to the resin of granular low density polyethylene (LDPE) (LDPE), high density polyethylene (HDPE) (HDPE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer polyolefins such as (EEA).
And, be not limited to these, in addition, so long as polycarbonate resin (PC), polyethylene terephthalate resin (PET), acrylonitrile-butadiene-styrene (ABS) (AB S) etc. have the character of the heat flow by heating and material that usually can extrusion molding, then can adopt with being not particularly limited.And, these thermoplastic resins also can mix two kinds with on use.
On the other hand; host as thermal plastic high polymer; as long as use PLA (PLA), poly butylene succinate (Poly (butylene succinate) (PBS)), polycaprolactone (PCL) to wait material, then can obtain to have its character that all is reduced into soil and from protecting the preferable polymer composite in aspect of environment with biological degradability.And, adopt the ECM Masterbatch (trade name) paid テ グ ラ ノ ボ Application (trade mark), Macrotec research company (U.S.) to wait the polyolefin-based resins of paying the additive of biological degradability, it seems preferable equally from the aspect of protecting environment.
As listing various known thermosetting resins such as epoxy resin, phenolic resins, unsaturated polyester resin, Lauxite, melmac, polyimides, diallyl phthalate, alkyd resins as the material of thermosetting polymer.
These thermosetting polymers can carry out polymerisation and make formed products by known curing agent being added in the host, keep to the shape of regulation and be set at solidification temperature.In addition, therefore the host of these thermosetting polymers can take liquid, solid, semisolid proterties because the monomer before the polymerisation is a low molecular weight compound, will be flow regime but improve temperature at least.
Therefore, under the melting temperature that is set to the temperature lower than solidification temperature, the host of thermosetting polymer and living beings origin composition are by mixing.
In these thermosetting polymers, alkyd resins is the synthetic high polymer that polyalcohol and polyacid polycondensation form, and this polyacid also (OH) forms ester bond with the hydroxyl on living beings origin composition surface in mixing process.Therefore, the compatibility at the interface between synthetic high polymer and the living beings origin composition is good, therefore can obtain fine and uniform dispersion structure.
As such polyalcohol, can enumerate propane diols, glycerine, trimethylolpropane, pentaerythrite etc.
As polyacid, can list phthalic anhydride, maleic anhydride, adipic acid etc.
And, as curing agent, can enumerate organic peroxide (benzoyl peroxide, cumyl peroxide etc.).
And, also can adopt epoxides to replace above-mentioned polyalcohol.In this case, epoxides is when mixing, and its 3 yuan of ring openings form the polyalcohol of divalent with on every side hydrone addition, promptly synthetic and the same alkyd resins of above-mentioned situation.In addition, when mixing unreacted epoxides after be set at solidification temperature and when forming formed products, 3 yuan of rings ring-opening polymerisation and form epoxy resin.
As the opportunity of in mixing operation, dropping into polyacid, preferably drop into earlier than polyalcohol (or epoxides), chemical reaction (esterification) takes place in surface preferential and living beings origin composition.Reason is that thus, the surface of living beings origin composition is modified, and can expect further to improve synthetic high molecular compatibility.Like this,, make the superfluous moisture thing of living beings origin composition and a part of polyacid generation chemical reaction and carry out after the surface modification, drop into remaining polyacid and polyalcohol (or epoxides) again and carry out mixing at the leading portion of mixing operation.
In addition, the opportunity of dropping into curing agent can be in the first half of mixing operation, arbitrary moment of front and back of back one half-sum dehydration procedure, but derives optimum condition by experiment.
As can be as the material of wax, be when being solid and heating at normal temperatures under than the low temperature of the host of synthetic high polymer fusion and the low organic compound of viscosity.This wax (C) extracts from natural goods, or industry is synthetic, but preferably the carbon number of the main chain of the chain hydrocarbon in the organic compound is included in material in 10～100 the scope.
Wax than the host elder generation fusion of synthetic high polymer, forms blended liquid phase with water in mixing operation.Therefore, the viscosity of mixing thing reduces, and the burden of mixing parts 50 alleviates and the raising of mixing property.And the wax of first fusion is adsorbed on the living beings origin composition, and promotes this living beings origin composition to be diffused in the molten mass of host of synthetic high polymer.
This carbon number was less than 10 o'clock, and the wax of fusion is gasification easily under melting temperature, can be discharged to the outside with water in dehydration procedure.
And carbon number is greater than 100 o'clock, and it is big that the viscosity of the wax of fusion becomes, and is difficult to form the blended liquid phase with water, can't contribute to improving mixing property.
The material that extracts from natural goods as in the wax can list saturated fatty acid.So-called saturated fatty acid is meant the monocarboxylic acid of chain hydrocarbon, is by CH 3(CH 2) nThe compound that the skeleton symbol of COOH is represented is applicable to that the n of being of the present invention is the compound more than 9.
This saturated fatty acid to be positioned at its terminal carboxyl (COOH) be hydrophilic group, the part (CH of chain hydrocarbon 3(CH 2) n) be hydrophobic group (lipophilic group).
Therefore, the hydrophobic group of the saturated fatty acid of fusion becomes the center, hydrophilic group form toward the outer side and water between the interface, form blended liquid phase easily with water.And, with the blended liquid phase of water in, saturated fatty acid forms globular micelle, therefore has at dehydration procedure to be difficult to along with water is discharged to outside feature.
And, with the globular micelle of saturated fatty acid in the blended liquid phase of water because mixing and miniaturization similarly is diffused in the whole mixing thing.When the carboxyl (COOH) of saturated fatty acid that is positioned at the surface of globular micelle contacted with living beings origin composition, esterification took place and carries out chemical bond (chemisorbed) in the hydroxyl surperficial with it (OH).
By such chemical reaction, the surface of living beings origin composition is by the saturated fatty acid chemical modification, and hydrophily disappears and the lipophile raising.Thus, living beings origin composition has the good character in the continuous phase of the host that is diffused into synthetic high polymer easily.
On the other hand, as the synthetic synthetic of the industry in the wax, can list single site catalysts polymerization by the metallocene catalyst representative olefin resin (particularly propylene system, ethene system).
As object lesson, can list the copolymer between homopolymers, these monomers and the alpha-olefin of the monomer of propylene or ethene.Also have, as alpha-olefin, can list ethene, 1-butylene, 1-amylene, 1-be alkene, 4-methyl-1-pentene, 1-heptene, 1-octene etc.Copolymer also can be any in block copolymer, random copolymer, the statistic copolymer.
In addition, wax also can mix the above-mentioned organic compound more than two kinds and uses.
The wax of the olefin resin that is polymerized by single site catalysts with compare being evenly distributed of the branch of side chain, molecular weight, crystal particle diameter by the situation of many site catalysts institute polymerization of Ziegler-Natta catalyst representative.
If adopt the wax of the olefin resin that is polymerized by single site catalysts, although the molecular weight ratio native paraffin is big, melt viscosity is low, therefore keeps good mixing property and the efficient discharge of water in dehydration procedure is contributed.
With respect to total amount 100 weight portions of above-mentioned synthetic high polymer and above-mentioned living beings origin composition, the use level of these waxes preferably is contained in the scope of 1～20 weight portion.
When the use level of wax is less than 1 weight portion, can't confirm the raising effect of mixing property, also can't confirm the efficient discharge effect of the water in the dehydration procedure.
On the other hand, the use level of wax is during more than 20 weight portions, and the mean molecule quantity of the polymer composite of manufacturing reduces, and the engineering properties of formed products reduces.
As the material that can be used as the superfluous moisture thing of living beings origin composition, can list and impregnated in afterwards dewatered living rice of stipulated time in the water, carry out the cereal that starch such as removal core or the also suitable corn that fitly is broken into a certain size such simple processing and obtains of epidermis, potato, sweet potato are.
The cereal of these starch system is being placed in the presence of the moisture more than the ormal weight under the common melting temperature Tz (100～200 ℃), and hydrone enters and causes the gelatinization that crystal structure destroys.Like this gelatinization starch (living beings origin composition) from the constraint of the mutual hydrogen bond of strand, free, therefore have fine easily and be distributed to character in the thermal plastic high polymer of fusion equably.
And, be provided with the water filling parts as long as drop into parts 12 as mentioned above like that, when putting into the cereal of these starch systems in the manufacturing installation 10 sometimes, suitably replenish the water filling that makes the required moisture of starch gelatinization, adjust superfluous moisture thing.
Then, as can be, can enumerate the lignocellulosic or be that the vegetation matter of main component is that living beings or chitins such as crab shell and shrimp shell are the suspension that miniaturization forms in water such as living beings with the cellulose of sening as an envoy to as the material of the superfluous moisture thing of living beings origin composition.Such suspension listed high-pressure homogenizer of enumerating and in water living beings being carried out the situation of physical crushing in can adopting above-mentioned patent documentation 2 also can be taked to carry out chemical treatment and the method that forms.In addition, the material that this so-called superfluous moisture thing constitutes except referring to add moisture like that artificially in living beings as mentioned above, also refer to originally just comprise the living beings of moisture itself,, all become object so long as contain in mixing operation the finally material of dehydrated moisture.
For example, adopt under the situation of timber as living beings, sometimes implement this timber is carried out the pre-treatment of mechanical crushing, making maximum gauge is the granular or sheet of the size about several mm, and the aggregate that timber can certainly be made the particulate of the size below several mm suitably adopts.In addition, as the aggregate of such particulate, also comprise the fiber plastid that extracts via chemical process from living beings.
We can say,, also can utilize hygroscopic effect and contain the superfluous moisture thing of tens wt%～tens wt% moisture even the micro powder body of these timber is not add moisture artificially.The micro powder body of such timber (or the rice skin etc.) can put in the manufacturing installation 10 with regard to former state without special operations such as drying processing.
Like this, living beings have the effect of the size of the maximum gauge about several mm, can list: even under a lot of situation of the water content of living beings, when dropping into parts 12 and biomass material is put into the manufacturing installation 10, also can prevent to stop up.
On the other hand, living beings be the particulate below several mm aggregate and since moisture absorption and water content a lot, drop under the situation that parts 12 take place to stop up, on the contrary, by making water logging in this aggregate and further increase water content artificially, can avoid stopping up.
Like this, further be dipped in the superfluous moisture thing of the living beings that just contain moisture originally by making water, except the above-mentioned effect of avoiding stopping up, the processing easy of the aggregate of the particulate that can also obtain to disperse easily, production efficiency improve such effect.
And the air that the aggregate of particulate includes is replaced as after the water, and is mixing with synthetic high polymer.Thus, the polymer composite of manufacturing can obtain that residual bubble reduces, defective tails off such effect.
In addition, the compatilizer that the compatibility between synthetic high polymer and the living beings origin composition will be improved further is sent to and drops in the parts 12.This compatilizer for example can adopt saturated carboxylic acid, unsaturated carboxylic acid or their derivative.And, also can use the material that makes the synthetic high polymer modification by the unsaturated carboxylic acid or derivatives thereof.
In addition, no matter inorganic, organic substance also can add silica or fibrous material etc., be distributed in the polymer composite these additive components are little.
Cylinder body 13 constitutes in the following manner: drop into interval A as upstream to have the raw material that drops into parts 12, having the part of taking out parts 17, be divided into C between mixing interval B, drying zone (C1, C2, C3), D between pressor areas again between this upstream and the downstream at least as downstream.And being used for cylinder body 13 inner settings being provided with on every side of cylinder body 13 is the heater (not shown) of melting temperature Tz (with reference to (c) of Fig. 1).
Mixing interval B is such interval: will carry out mixing from the host that drops into the synthetic high polymer that parts 12 drop into, the superfluous moisture thing and the compatilizer of living beings origin composition under the condition of authorized pressure and melting temperature Tz.Thus, the miniaturization in mixing thing of living beings origin composition, suitably with compatilizer generation chemical reaction, thus pay and synthetic high polymer between compatibility, be distributed to equably in the mixing thing.
C can further be divided into C2 between the interval C1 of pressurizing and dehydrating, normal pressure drying zone, the interval C3 of decompression dehydration between drying zone, and these intervals are respectively equipped with the dehydration part 40 (with reference to (b) of Fig. 1) more than 1 at least.
At this, the interval C1 of pressurizing and dehydrating is such part: shown in Fig. 1 (c), under condition lower than the saturated vapour pressure Pz under this melting temperature Tz and high setting pressure Pa, Pb than atmospheric pressure P0 the moisture that mixing thing comprised is dewatered.
By under such setting pressure Pa, Pb, carrying out processed, the water content that the limit makes mixing thing not sharp, reduce gradually, the limit is further mixing.Thus, be suppressed at miniaturization in the mixing thing and the reassociating and further carry out miniaturization, the decentralized of living beings origin composition that disperses.
C2 is such part between the normal pressure drying zone: shown in Fig. 1 (c), under the condition of the setting pressure Pc that approaches atmospheric pressure P0, Pd contained moisture in the mixing thing that has passed through the interval C1 of pressurizing and dehydrating is dewatered.By carrying out processed under the condition of such setting pressure Pc, Pd, the mixing thing limit that water content has reduced further reduces the water content limit gradually and further carries out mixing.Thus, be suppressed at miniaturization in the mixing thing and the reassociating and further carry out miniaturization, the decentralized of living beings origin composition that disperses.
The interval C3 of decompression dehydration is such part: shown in Fig. 1 (c), under the condition of the setting pressure Pe lower than atmospheric pressure P0 by forcing 30 pairs of decompressors to pass through that contained moisture dewaters in the mixing thing of C2 between the normal pressure drying zone.By carry out processed under such setting pressure Pe, the moisture major part that mixing thing comprised is removed.
In addition, the vacuum that the interval C3 of decompression dehydration connects is coagulated air valve 31 and is used for the steam of cool gasification and reverts to liquid, and the saturated steam that prevents high temperature enters into forces decompressor 30 to suppress to force decompressor 30 deteriorations.
Like this, by the saturated vapour pressure Pz of pressure under melting temperature Tz that pays mixing thing dewatered after reducing step by step, can suppress reassociating of living beings origin composition, and the miniaturization of promotion living beings origin composition, decentralized.
D is such position between pressor areas again: the mixing thing after continuing processed finished carries out mixing, and pressurizes and pay from taking out parts 17 and take out needed pressure.Thus, the molten mass of the polymer composite that disperses imperceptibly of living beings origin composition is removed from taking out parts 17.
Screw rod 15 is formed with spiral helicine step 16 around its axostylus axostyle, by rotating around axis, step 16 is paid pressure and mixing thing is extruded towards the downstream from the upstream of cylinder body 13.
Shown in the partial sectional view of Fig. 1 (b), dehydration part 40 contains filter 41, isolated wall 42 and voltage regulation part 45 and constitutes.
The dehydration part 40 of Gou Chenging is used for paying setting pressure Px (x=a, b, c, d, e) arbitrarily by the mixing things in 45 pairs of cylinder bodies of voltage regulation part 13 like this, and this setting pressure Px is lower and than atmospheric pressure P 0 height than the saturated vapour pressure Pz under the melting temperature Tz.Thus, dehydration part 40 can make moisture contained in the mixing thing not sharp, little by little dewater.
Filter 41 is configured to sealing and is set at opening on the wall of cylinder body 13, is used for separating the inside and the moisture outside and that optionally filter mixing thing and contained thereof of cylinder body 13.As the structure of such filter 41, can list and on the plate face, be provided with the structure that a plurality of holes, this plate face are fixed along the internal face of cylinder body 13.
Isolated wall 42 is used to form the gasification space V that makes the moisture gasification that is filtered plate 41 filtrations and makes this gasification space V and atmospheric isolation.As the structure of so isolated wall 42, the container that can list the end is fixed, further makes filter 41 butts in the roughly consistent mode of its opening and the opening on being arranged on cylinder body 13 and the structure that filter 41 is fixing.
Voltage regulation part 45 is made of pressure gauge 43 and choke valve 44, be used for the air pressure of gasification space V is set at the setting pressure Px (x=a, b, c, d, e) of regulation, this pressure gauge 43 is used to measure the air pressure of gasification space V, and this choke valve 44 is used for changeably to paying flow resistance by isolated wall 42 to the gas (steam) that atmospheric side discharges from gasification space V.
By suitably regulating the amount of restriction of this choke valve 44, the air pressure of gasification space V can be set at from the saturated vapour pressure Pz under the melting temperature Tz to the numerical value arbitrarily the atmospheric pressure P0.That is to say that if choke valve 44 fully cuts out, the air pressure of gasification space V is set to this saturated vapour pressure Pz,, then be set to atmospheric pressure P0 if choke valve 44 is fully opened.Further be connected, the air pressure of gasification space V can be set at below the atmospheric pressure P0 with forcing decompressor 30.
In addition, this voltage regulation part 45 makes this setting pressure Px approach to take out parts 17 more in being arranged at a plurality of dehydration parts 40 of cylinder body 13 and sets more littlely that (Pa＞Pb＞Pc), this is best suppressing aspect the reassociating of living beings origin composition as stating.
And the mode that setting pressure Px is not discharged by gasification with the aqueous reagent that is dropped into suitably is set at moisture and preferentially is discharged from.
Then, (P0＞Pe) can make from taking out the mixing thing that parts 17 extrude and dewater more completely by the dehydration part 40 that is positioned at downstream in a plurality of dehydration parts 40 that are set on the cylinder body 13 being set as the setting pressure Pe lower than the pressure of atmospheric pressure P0.
(action specification of manufacturing installation)
Then, with reference to Fig. 1 (a), Fig. 1 (b) and as (c) of Fig. 1 of the state diagram of water the action of manufacturing installation 10 and the function of dehydration part 40 are described.
The superfluous moisture thing of the host of synthetic high polymer, living beings origin composition and other necessary compositions (wax, compatilizer etc.) are put to the inside of manufacturing installation 10 by dropping into parts 12, and be mixing by mixing parts 50 under the melting temperature of setting.So, the water of activation enters between the strand of living beings and makes this intermolecular combination loosening.And, to utilize by the mixing mechanical energy of paying, living beings ftracture and carry out miniaturization.
And, fusion wax and water form low viscous blended liquid phase, the viscosity of mixing thing integral body reduced and improve mixing property, and be adsorbed on the surface of living beings origin composition.And other compounds (compatilizer, aliphatic acid, polyacid etc.) with carboxyl are by the dehydration (ester reaction) shown in the following formula (3), and the hydroxyl (OH) on living beings origin composition surface (R ') is replaced into the substituting group with ester bond.Thus, the hydrophily of living beings origin composition reduces, and dies down with combining of moisture, can realize dewatering efficiently in next dehydration procedure.
[Chemical formula 1]
Figure G2008800142946D00151
Arrival is arranged in the mixing thing of dehydration part 40a of the upstream that is set at cylinder body 13 under the effect of the pressure of paying from screw rod 15, is given as security to lean against on the filter 41, and contained moisture optionally passes through this filter 41, is accumulated among the gasification space V.The melting temperature that is accumulated in the moisture among this gasification space V is Tz, in the gasification space V that is set to the pressure Pa lower than its saturated vapour pressure Pz, and this moisture of accumulating gasification.The moisture of this gasification (steam) is discharged into the atmosphere by the choke valve 44 of voltage regulation part 45.
Therefore in this dehydration part 40a, the pressure reduction between setting pressure Pa and the atmospheric pressure P0 is little, and the dehydration of mixing thing is not carried out sharp, just becomes the state that water content reduces, and is expressed among the dehydration part 40b in downstream by mixing the time.
Even in next dehydration part 40b, the moisture of accumulating in being set to the gasification space V of the pressure P b lower than saturated vapour pressure Pz is discharged into the atmosphere by gasification similarly.
Below, same repeatedly action in the dehydration part 40 that is arranged at the downstream (40c, 40d, 40e) like this, mixing thing dewaters gradually step by step and by mixing, therefore can suppress reassociating of living beings origin composition.
Then; the mixing thing that dehydration has been finished is with the form of the molten mass of the polymer composite that is dispersed with living beings origin composition; from take out parts 17, be removed, and be configured as (polymeric composite compositions) such as particles of grain of rice shape by comminutor (omit and illustrate) etc.
This particle is reheated and after the fusion, be injected in the mould and form block formed products, perhaps carry out stretch process (for example plavini, calendering processing method, T-punch die method, blow moulding etc.) and form the formed products of sheet, or form expansion-molded article by foaming, can be as the raw material of making common Process Technology of Polymer formed products.
In addition, can directly not make such formed products by the molten mass of the polymer composite of from take out parts 17, extruding via the shaping of such particle yet.
Above embodiment is to be used to illustrate an example of the present invention, the invention is not restricted to above-mentioned embodiment, can carry out various distortion in the scope of the purport of inventing.For example, manufacturing installation 10 does not need to be provided with especially C2 and the interval C3 of decompression dehydration between the normal pressure drying zone sometimes as long as be provided with the interval C1 of pressurizing and dehydrating at least.Reason is that (making the moisture gasification) this situation of under melting temperature Tz, can dewatering is fully confirmed fully from the state diagram of the water of Fig. 1 (c) under the pressure higher than atmospheric pressure P0.
And, the subregion of illustrated cylinder body 13 (A, B, C1, C2, C3, D) is to illustrate, also can be the subregion that other suitably are set between these subregions (for example, between the interval C3 of C2 and decompression dehydration between the normal pressure drying zone, mixing interval B is set, a plurality of raw materials are set drop into interval A etc.).
Other such concrete example application are illustrated.Drop into living beings (thing etc. that is untreated of the crushed material of timber or rice husk) and compatilizer from dropping into parts 12, it is mixing with both to drop into interval A at the 1st raw material.Drop among the interval A at this raw material, living beings are further by pulverizing and micronize, and compatilizer is adsorbed on the surface of living beings, improve the compatibility with the synthetic high polymer that drops into afterwards.
Then, drop in interval (not shown), drop into host and other reagent that needs of synthetic high polymer at the 2nd raw material, mixing with living beings.Thus, living beings origin composition is fine and be distributed to equably in the continuous phase of synthetic high polymer.
In addition, as the structure of manufacturing installation 10, between drying zone C1, C2, C3 can take to be arranged in the 1st raw material drop into interval A and the 2nd raw material drop into middle the operation of interval (end diagram) situation, be positioned at arbitrary situation of situation that the 2nd raw material drops into the back operation in interval (not shown).In addition, also can take the centre of arbitrary intervals to append the situation of mixing interval B.
The 2nd embodiment
Below, with reference to the longitudinal section shown in Fig. 2 (a), the 2nd embodiment of the manufacturing installation of polymer composite of the present invention is described.In addition, part identical or suitable with Fig. 1 in (a) of Fig. 2 is represented with same Reference numeral, quotes existing record, omits detailed explanation.
The manufacturing installation 10 ' of the 2nd embodiment is applicable to following situation: the superfluous moisture thing as the living beings origin composition of the raw material of polymer composite, adopted the many and mobile high material of the such water content of suspension.
Such manufacturing installation 10 ' its structure is characterised in that, adopted superfluous moisture thing with living beings origin composition to be pressed into the pressing parts 20 of inside of cylinder body 13 and the screw rod 15 ' this point that the diameter of axle changes.And the interval that the raw material of polymer composite is dropped into is divided into the interval A 1 of host input that the host of synthetic high polymer dropped into and is set at this host drops into the suspension that the suspension of the superfluous moisture thing of the downstream of interval A 1 and living beings origin composition dropped into and drops into interval A2.
Pressing parts 20 is connected via the inlet 14 of the interval A2 of the suspension input that is arranged on cylinder body 13, and it comprises: the liquid storing part 21 that is filled with the superfluous moisture thing of living beings origin composition; Pay the superfluous moisture thing of living beings origin composition is injected into the motor 22 of the driving force the cylinder body 13 from this liquid storing part 21; Prevent the check-valves 24 of adverse current of the superfluous moisture thing of the living beings origin composition that this is injected into; And the choke valve 25 of regulating the injection rate of the superfluous moisture thing that is injected into the living beings origin composition in the cylinder body 13.
In addition, near the inside of the cylinder body 13 this inlet 14 is in the pressurized state of the mixing thing of synthetic high polymer, so pressing parts 20 need be at the superfluous moisture thing that is pushed down into living beings origin composition than this bigger pressure.And, the heater block that heats superfluous moisture thing also can suitably be set on pressing parts 20, make the moisture thing of bulged-in surplus not reduce the temperature of mixing thing.
Suppose, the manufacturing installation 10 of superfluous moisture image the 1st embodiment of so mobile high living beings origin composition mixed with synthetic high polymer like that and when putting into cylinder body 13, both might separate in the inside of dropping into parts 12, the cooperation rate variable of living beings origin composition, mixing deposits yields cooperates the inhomogeneous of ratio.But, be pressed into by superfluous moisture thing as the manufacturing installation 10 ' of the 2nd embodiment from the inlet 14 that is arranged on the downstream living beings origin composition that flowability is high, can be all the time with constant ratio and unevenly living beings origin composition is not put in the mixing thing.
Then, the material that is pressed into from pressing parts 20 is not limited to the superfluous moisture thing of above-mentioned living beings origin composition, for example also is pressed into aforesaid polyacid, polyalcohol, the so various aqueous reagent that cooperates in mixing operation of organic peroxide sometimes.
And pressing parts 20 is not limited to dispose as shown in Figure 2 single, disposes a plurality ofly sometimes according to purpose, and the position of configuration also is not limited to the upstream of dehydration part 40, also is configured in the downstream of dehydration part 40 sometimes.Reason is that aqueous reagent as described above is pressed in the mixing thing after being preferably in and fully dewatering.
Secondly, at the position that is provided with of the dehydration part 40 (40a, 40b, 40c, 40d) that is arranged at C2 between interval C1 of pressurizing and dehydrating or normal pressure drying zone, the diameter of axle of screw rod 15 ' forms bigger than the diameter of upstream side.By such formation screw rod 15 ', mixing thing further pressurizes than upstream side, and the capacity of mixing thing reduces even the moisture that contains is removed, and also can keep the pressure that this mixing thing is paid at least.
And at the position that is provided with of the dehydration part 40 (40e) that is arranged at the interval C3 of decompression dehydration, the diameter of axle of screw rod 15 ' forms littler than the diameter of upstream side.By such formation screw rod 15 ', mixing thing is in this interval, and the pressure of mixing thing being paid from screw rod 15 ' is disengaged (decompression), and mixing thing forms the low pressure lower than atmospheric pressure P0, the promotion dehydration.
And, passing through again between pressor areas among the D of C1, C2, C3 between drying zone, screw rod 15 ' the diameter of axle form bigger than the diameter of upstream side.By such formation screw rod 15 ', the mixing thing through dewatering is pressurizeed in this interval again and is taken out from take out parts 17.
And the example that in the explanation of the 2nd above-mentioned embodiment, the host that shows synthetic high polymer puts into the inside of cylinder body 13 from dropping into parts 12, the suspension that comprises living beings origin composition is put into the inside of cylinder body 13 from pressing parts 20.
Other example application as the 2nd embodiment, sometimes host and the starchiness with synthetic high polymer is that living beings (giving birth to rice etc.) are put into the inside of cylinder body 13 from dropping into parts 12, pressing parts 20 is injected into water as the water filling parts inside of cylinder body 13.
In this case, pressing parts 20 can adopt the common supply hot water parts with the function of regulating flow and temperature.Then, starchiness is living beings (give birth to rice etc.) with the host of synthetic high polymer by mixing and absorb the water that is injected into and become superfluous moisture thing, carries out gelatinization then.
(the 3rd embodiment)
Below, with reference to the longitudinal section shown in Fig. 2 (b), the 3rd embodiment of the manufacturing installation of polymer composite of the present invention is described.Also have, part identical or suitable with Fig. 1 and Fig. 2 (a) in (b) of Fig. 2 is represented with same Reference numeral, quotes existing record, omits detailed explanation.
The manufacturing installation 10 of the 3rd embodiment " be applicable to following situation in the same manner with the situation of the 2nd embodiment; promptly, adopted the many and mobile high material of the such water content of suspension as situation as the superfluous moisture thing of the living beings origin composition of the raw material of polymer composite.
And, manufacturing installation 10 " structure be characterised in that the screw rod 15 that has adopted the spacing of step 16 to change " this point.
Towards the downstream of screw rod 15, during the pitch smaller of step 16, the pressure of paying mixing thing increases along with like this, and when opposite spacing became big, the pressure of paying mixing thing reduced.
Therefore, at the dehydration part 40 (40a, 40b, 40c, 40d) that is arranged at C2 between interval C1 of pressurizing and dehydrating or normal pressure drying zone position, screw rod 15 be set " the spacing of step 16 form spacing less than upstream side.And, at the dehydration part 40 (40e) that is arranged at the interval C 3 of decompression dehydration position, screw rod 15 be set " the spacing of step 16 form spacing greater than upstream side.
By such formation screw rod 15 ", under the condition identical with the situation of the 2nd embodiment, mixing thing is pressurized or be depressurized in the position that is provided with dehydration part 40, promotes the dehydration of mixing thing step by step.
(the 4th embodiment)
Then, with reference to cutaway view shown in Figure 3, the 4th embodiment of the manufacturing installation of polymer composite of the present invention is described.The manufacturing installation 10 of above-mentioned Fig. 1 and Fig. 2 is continous way devices that each operation of taking-up operation of the input operation of carrying out raw material incessantly simultaneously, mixing operation, mixing thing is made polymer composite continuously.Relative therewith, each operation such as taking-up operation that the manufacturing installation 60 of the 4th embodiment carries out the input operation of raw material, mixing operation, mixing thing is respectively in order repeatedly made the batch (-type) device of polymer composite intermittently.
This manufacturing installation 60 comprises input parts 12 (hopper), mixing parts 62 and dehydration part 40.At this, mixing parts 62 comprise driver part (not shown), housing 63 and rotor 65.
And (a)～(c) of Fig. 3 is the cross section with the rotating shaft direct cross of rotor 65, and expression is along the cutaway view of the manufacturing installation 60 of its length direction difference (comprise respectively drop into parts 12, dehydration part 40, take out parts 67).
Also have, in Fig. 3, the part identical or suitable with Fig. 1 represented with same Reference numeral, quotes existing record, omits detailed explanation.
Comprise housing 63 and rotor 65 in the structure of mixing parts 62, be used under the melting temperature of setting that the superfluous moisture thing of host, living beings origin composition of the synthetic high polymer that will drop into and other materials stir and mixing, form fine and uniform polymer composite.
Housing 63 be provided with the host that drops into synthetic high polymer and living beings origin composition superfluous moisture thing input parts 12 and mixing thing is fetched into outside taking-up parts 67.
These input parts 12 open and close parts 61 via the 1st and are connected with the mixing space W of housing 63 inside, when the 1st switching parts 61 are set as " opening state ", the host of synthetic high polymer and the superfluous moisture thing of living beings origin composition can be put into the mixing space W from dropping into parts 12.On the other hand, when the 1st switching parts 61 were set as " closing state ", the gas flow of circulation also was cut off between mixing space W and input parts 12.
Take out parts 67 and be connected with the mixing space W of housing 63, when the 2nd switching parts 68 are set as " opening state ", can take out the mixing thing that is in the mixing space W via the 2nd switching parts 68.On the other hand, when the 2nd switching parts 68 were set as " closing state ", the gas flow of circulation also was cut off between mixing space W and taking-up parts 67.
Like this, open and close parts 61 and the 2nd with the 1st and open and close parts 68 when being set as " closing state ", mixing space W becomes enclosure space, and mixing space W is maintained at saturated vapour pressure the Pz (＞P0: atmospheric pressure) (with reference to (c) of Fig. 1) under the melting temperature Tz of setting.
Rotor 65 is used for making mixing thing mixing in the mixing space W rotation that forms enclosure space and be set to the housing 63 of melting temperature.In Fig. 3 illustrated this rotor 65 to extrude the mode of mixing thing and be rotated in order to involve in reverse each other two rotary bodies of direction of rotation from the input thing that drops into parts 12 and to taking out parts 67, but be not limited to such embodiment, can use known rotor.
Shown in Fig. 3 (b), dehydration part 40 is set on the opening that runs through the mixing space W of being located at housing 63, is used to regulate the pressure of enclosure space, and utilizes the pressure after this adjusting to carry out the dehydration of mixing thing.
Filter 41 is used to separate the mixing space W and the outside of housing 63, and optionally filters the moisture that is contained in the mixing thing.
Isolated wall 42 is formed with the gasification space V that is connected with mixing space W via filter 41, and is provided with voltage regulation part 45.
Voltage regulation part 45 is used to regulate the air pressure of the mixing space W that forms enclosure space and is set at setting pressure, has pressure gauge 43 and choke valve 44.
In addition, the dehydration part 40 of Fig. 3 (b) is identical with the dehydration part shown in (b) of Fig. 1, but in the manufacturing installation 60 of present embodiment, also play and the identical effect of gasification space V that is communicated with on the top of mixing space W.Therefore, also can take not to be provided with filter 41 and isolated wall 42 and the direct structure that voltage regulation part 45 is set on housing 63.
And, though not shown in Fig. 3, in manufacturing installation 60, also can take to be provided with the structure of pressing parts 20 (with reference to Fig. 2).
(action specification of manufacturing installation)
Then, with reference to Fig. 3, carry out the action specification of manufacturing installation 60.
The 1st switching parts 61 form " opening state ", the 2nd switching parts 68 form " closing state ", by dropping into parts 12 with the host of synthetic high polymer, the superfluous moisture thing of living beings origin composition and the inside that other compositions (wax, compatilizer etc.) that needs are put into manufacturing installation 60.Then, opening and closing parts 61 with the 1st is set as " closing state " and will drops into thing and be set at melting temperature and undertaken mixing by mixing parts 62.
Then, make voltage regulation part 45 actions in good time, make the moisture that is in mixing space W become steam, be discharged into the outside, the aqueous reagent that perhaps never illustrated pressing parts 20 (with reference to Fig. 2) input needs.And, force down, fully dewater by forcing decompressor 30 (with reference to (a) of Fig. 1) to make mixing space W reduce pressure as required than atmosphere.
Then, open and close parts 68 with the 2nd and be set as " opening state ", from take out parts 67, take out the mixing thing in the mixing space W.By above repeatedly operation, produce polymer composite in batches.
As manufacturing installation 10,10 ', 10 by above-described polymer composite ", the host of 60 mixing synthetic high polymers, can adopt in thermal plastic high polymer and the thermosetting polymer any.And, for the reagent in the host of suitably adding these synthetic high polymers to (curing agent that comprises thermosetting polymer),, can adopt known reagent at its kind, proterties, adding method.And, with the parts that such reagent mixes with host, be not limited to the parts of illustrational embodiment, can adopt only parts according to example.
And order that is dropped into and opportunity and the number of times of implementing dehydration are arbitrarily from dropping into parts 12 for the superfluous moisture thing of the host of synthetic high polymer, living beings origin composition and other compositions (wax, compatilizer etc.) that needs.
That is to say, except all being put into, mentioned component carries out in the machine the situation mixing, that dehydration is then taken out, for example, also can take following situation: the superfluous moisture thing and the compatilizer that drop into living beings origin composition carry out mixing, dehydration in advance, the host that drops into synthetic high polymer is then carried out mixing, takes out mixing thing again.
＜about the living beings concentrated phase body of polymer composite 〉
As long as prepare the living beings concentrated phase body of the polymer composite that is combined with living beings origin composition in high proportion in advance, it is mixing with synthetic high polymer, and the concentration that just can at random dilute living beings origin composition is made resin forming product.
And, adopt such manufacture method, can not be mingled with moisture ground and produce the composite that evenly is dispersed with living beings origin composition in batches.And, do not need to have the special manufacturing installation 10 of above-mentioned such dehydration part 40, can utilize common building mortion to produce biomass composite easily in batches.
And, when living beings origin composition is placed with monomer, because surface oxidation, reduce with the compatibility of synthetic high polymer, if but be configured as this concentrated phase thing, and because being synthesized macromolecule, the particle of living beings origin composition covers, worsen so be difficult to carry out the material of oxidation etc.
Below, the living beings concentrated phase body (being designated hereinafter simply as " concentrated phase body ") that is suitable for diluting like that the polymer composite that uses is most described.In addition, the synthetic high polymer that is contained in this living beings concentrated phase body is defined as the 1st synthetic high polymer, is defined as the 2nd synthetic high polymer diluting used synthetic high polymer afterwards.
As the synthetic resin that can be used as the 1st synthetic high polymer, there is no particular limitation, but preferably use olefin resins such as propylene resin and vinylite.
There is no particular limitation for the polymerization methods of these propylene resins and vinylite, the degree of polymerization also comprise monomer in conjunction with number for from 10 to less than 100 oligomer (wax), surpass 100 polymer the two.
Then, in order to make the composite that living beings origin composition forms even and fine decentralized photo, the polymerization methods of the single site catalysts that the free degree that best the 1st synthetic high polymer employing has utilized MOLECULE DESIGN is high is synthesized with the degree of polymerization with melting temperature characteristic described later.
Characteristic as the 1st synthetic high polymer institute that constitutes this concentrated phase body should possess can list under the melting temperature of manufacturing concentrated phase body, has good flow behavior.
For the 1st synthetic high polymer the crystalline polymer in the above-mentioned thermoplastic resin that can adopt, can be with by differential scanning calorimeter (DSC; DifferentialScanning Calorimetry) melting temperature of Ce Lianging is as the index of estimating flow behavior.
That is to say, the temperature of crystalline polymer is changed continuously, and detect the crystallization fusion and the heat of transformation when solid is varied to liquid, can know the solid-liquid ratio of the 1st synthetic high polymer under the arbitrary temp by DSC.
And generally speaking, under arbitrary temp, liquid fraction is high more, all is under the situation of liquid, and the fusion peak is in low temperature, the low and mobile excellence of viscosity more.
In addition, for the amorphism macromolecule in the thermoplastic resin, owing to can't observe the such fusion phenomenon of crystalline polymer, therefore can adopt glass transition temperature by dsc measurement as the index of estimating flow behavior.
Being in the 1st synthetic high polymer of main component with propylene resin as crystalline polymer, it is desirable to, be included in by the melting temperature of dsc measurement in 50 ℃～150 ℃ the scope.
Being in the 1st synthetic high polymer of main component with vinylite as crystalline polymer, it is desirable to, be included in by the melting temperature of dsc measurement in 50 ℃～120 ℃ the scope.
At this, so-called melting temperature is meant from begun the temperature range of temperature T im to fusion end temp Tem by the determined fusion of JISK7121.
When the fusion of the 1st synthetic high polymer begins temperature T im less than the lower limit (50 ℃) of said temperature scope of regulation, sometimes the 1st synthetic high polymer is in the ground fusion of common serviceability temperature (normal temperature) lower part, has the sensation that is clamminess as the surface of the biomass composite of final products.
In addition, when the fusion end temp Tem of the 1st synthetic high polymer is higher than the high temperature of the upper limit of said temperature scope of regulation, sometimes under the melting temperature of the synthetic resin of common same system, the residual part that fusion is arranged not comprises internal flaw sometimes as the biomass composite of final products.
For the melting temperature of temperature range with such regulation, the 1st synthetic high polymer preferably carries out the olefin resin (propylene resin, vinylite) of polymerization by above-mentioned single site catalysts.
Reason is that the melting temperature of these crystalline polymers is configured with relation closely with this high molecular one dimension, and it is preferable therefore to carry out polymerization by the single site catalysts that can critically control the one dimension structure.Can the such situation of realization think to have single character owing to the part relevant of this single site catalysts with polymerisation by the one dimension of accurate control structure, so the polymerisation homogenising.
Under the synthetic situation of single site catalysts, and compare by the synthetic situation of the multicenter catalyst of Ziegler-Natta catalyst representative, the branch that waits side chain seldom, the olefin resin of being evenly distributed of molecular weight, crystal particle diameter is aggregated.Therefore, can obtain in the temperature range arbitrarily that scope comprised that melting temperature by dsc measurement is in regulation and the sharp-pointed olefin resin (the 1st synthetic high polymer) of shape at fusion peak.
At this, the carbon number that the 1st synthetic high polymer is contained the main chain of chain hydrocarbon is contained in the situation of the wax in 10～100 the scope and investigates.This wax is the synthetic synthetic resin of industry, or the natural resin that extracts from natural goods, all is solid at normal temperatures, heating and after the fusion, demonstrate the viscosity lower than the 2nd synthetic high polymer.Therefore, the concentrated phase body that is combined with this wax mixes with the 2nd synthetic high polymer and when mixing, the fusion of going ahead of the rest of wax composition.So, the viscosity of mixing thing reduces, and the burden of kneading device reduces and the raising of mixing property, and living beings origin composition evenly and imperceptibly is distributed in the 2nd synthetic high polymer continuous phase.
At this, the carbon number of the main chain of wax was less than 10 o'clock, and the fusing point of wax is a low temperature, is shown as liquid at normal temperatures, and the surface of the living beings resin of manufacturing has the sensation that is clamminess.
And the carbon number of the main chain of wax was greater than 100 o'clock, and the fusing point of wax is a high temperature, and it is big that melt viscosity becomes.So, the dispersiveness of living beings origin composition in the continuous phase of the 2nd synthetic high polymer reduces.
As wax, can list the wax of saturated fatty acid as natural resin.
So-called saturated fatty acid is meant the carboxylic acid of the monobasic of chain hydrocarbon, is CH 3(CH 2) nThe compound that the skeleton symbol of COOH is represented is applicable to that preferably the n of being of the present invention is the saturated fatty acid more than 9.
Its terminal carboxyl (COOH) that is positioned at of this saturated fatty acid is a hydrophilic group, the part (CH of chain hydrocarbon 3(CH 2) n) be hydrophobic group (lipophilic group).
Therefore, the carboxyl of the end of saturated fatty acid (COOH) carries out chemical bond (chemisorbed) with the hydroxyl (OH) on living beings origin composition (R) surface by the dehydration shown in the following formula (ester reaction).
[Chemical formula 2]
Figure G2008800142946D00271
By such chemical reaction, the hydroxyl (OH) on the surface of living beings origin composition is carried out chemical modification by saturated fatty acid, and hydrophily disappears, and lipophile improves.Thus, the decentralized photo of living beings origin composition has the good character that is diffused into easily in the 2nd synthetic high polymer continuous phase.
As the wax of synthetic resin, preferably utilize the olefin resin of above-mentioned single site catalysts polymerization.Like this, under the situation of the wax phase of natural resin contrast, be not only long-chain and have the high feature of hardness, therefore can obtain the composite of the living beings resin of mechanical property excellence with same melting point (or melt viscosity).
And, under the situation about comparing with other synthetic waxs (ziegler-natta catalyzed method, high-pressure process etc.) of the hardness with same degree, also have the feature that fusing point is low and viscosity is low by the wax of the olefin resin of single site catalysts polymerization.
As the living beings origin composition that constitutes the concentrated phase body, can list with amylose or amylopectin is that the starchiness of main component is living beings, is that the vegetation matter of main component is that living beings, the chitin that derives from shellfish (or shitosan) are living beings (crab shell, shrimp shells etc.) with lignocellulosic or cellulose, wherein, described amylose is that glucose passes through α-1,4 glycosidic bonds and be combined into that the straight chain shape forms, described amylopectin has α-1 on branch, the two straight chain of 4 glycosidic bonds and α-1,6 glycosidic bond.
When making the concentrated phase body, be the pre-treatment of living beings, remove core or epidermis and fitly be broken into a certain size or append the simple processing of the required such degree of moisture of gelatinization just enough as these starchiness.The starchiness that has carried out so simple processing be living beings with the 1st synthetic high polymer when mixing, the moisture that the starch utilization contains in this process and gelatinization, miniaturization, and be distributed to equably in the 1st synthetic high polymer.
In addition, this moisture that contains is discharged from the dehydration part that is arranged on the kneading device in the back operation of the mixing operation of making the concentrated phase body.
And, the starchiness that raw material adopted as the concentrated phase body is living beings, be not limited to implement like this cereal of simple pre-treatment, also can be, from these cereal, extract material that the composition of amylose or amylopectin forms as raw material with known method with the cereal by known method gelatinization in advance (taking the starch of amorphous structure).
And, derive from employing under the situation of living beings origin composition of starch, in order to promote its miniaturization, when making the concentrated phase body, add amylase sometimes.
This amylase is that molecular weight is approximately 55000 enzyme, and AMS, beta amylase, glucoamylase are arranged, and all is industrial mass-produced enzyme.
AMS cuts off the α-1 of starch brokenly, 4 glycosidic bonds and be hydrolyzed into polysaccharide or oligosaccharides, beta amylase cuts off starch and resolves into maltose with 2 glucose units from end, glucoamylase cut off sugar chain non-reduced end α-1,4 glycosidic bond and resolve into glucose.
And isoamylase, amylopectase optionally cut off the glycosidic bond as the α of the component of carbohydrate-1,4.
Wherein, AMS is preferable from the aspect of the miniaturization of the living beings origin composition that promotes to derive from starch.And isoamylase, amylopectase are owing to the low-molecular-weightization that prevents living beings origin composition, and be therefore preferable.
But, in the scope of 40 ℃～80 ℃ of hydrogen ion exponent pH5～pH7, temperature, the enzymatic activity of AMS is kept than the highland.
Therefore, when making the concentrated phase body, amylase be put to starchiness be can take on opportunity in the living beings starch be living beings be put to before the kneading device, simultaneously, arbitrary moment afterwards, but need keep the condition of not losing diastatic enzymatic activity.
Particularly, be when living beings are put to kneading device or drop into afterwards under the diastatic situation that at starchiness melting temperature need be set at the scope of not losing enzymatic activity.In this case, the melting temperature of the 1st synthetic high polymer that is dropped into also preferably is low to moderate such degree that flows fully in the temperature range of not losing enzymatic activity.
When exceeding the scope of diastatic reactive conditions, diastatic enzyme denaturation and inactivation, particularly at high temperature, underspeeding of diastatic activity accelerates sharp.Give one example, have such report example: the residual activity when having placed 20 minutes under 70 ℃ is 90%, and the residual activity when having placed 20 minutes under 75 ℃ is reduced to 50%.
In addition, be living beings 100 weight portions with respect to starchiness, diastatic addition is 0.001～5 weight portion preferably.At this, under the situation of diastatic addition less than 0.001 weight portion, the decomposition rate of starch is slack-off, under the situation more than 5 weight portions, too promotes the decomposition of starch, and living beings origin composition becomes low-molecular-weight, and is not good.
Starchiness is living beings as long as decomposed by diastatic enzymatic activity, also promotes the gelatinization reaction, and living beings origin composition is fine and be distributed to equably by in the 1st mixing together synthetic high polymer.
Like this, with the AMS after the amylase decomposition is unwanted, but does not have selectivity to remove the parts of this AMS, therefore can be blended in the concentrated phase body at that, perhaps melting temperature is set as high temperature and makes its thermal denaturation, sneak into to have suppressed active state.
On the other hand, as being that living beings are the material of raw material with vegetation, specifically, can list thinnings as the discarded object of timber industry and pulp industry etc., building disintegration material etc., straw, beanpod shell, waste paper, wood chip, wood powder, sawdust, wood shavings, bamboo powder, bagasse, fruit shell powder, cotton, artificial silk (rayon) etc. through pulverization process as agricultural wastes.And, these shapes are had no particular limits, can use fibrous, pulverous material.
And also can suitably utilize following material: adopting high-pressure homogenizer is that living beings and chitin be that living beings carry out physical crushing or make these vegetation matter by chemical treatment in water are that living beings and chitin are that the living beings miniaturization forms suspension to these vegetation matter in water.
And, in order to relax these living beings origin composition gatherings each other, when making the concentrated phase body, add alkali metal salt sometimes.
There is no particular limitation for the kind of alkali metal salt, but can list alkali carbonates such as lithium carbonate, sodium carbonate, potash, cesium carbonate, can also list alkali earth metal salts such as brium carbonate, calcium carbonate, strontium carbonate.
When these alkali metal salts are added, when making the concentrated phase body, utilize the compatibility of alkali metal ion and living beings origin composition, the cohesive force between living beings origin composition dies down, and living beings origin composition improves with respect to the dispersiveness of the 1st synthetic high polymer.
And after making the concentrated phase body, in storage, prevent miniaturization living beings origin composition reassociate.And with concentrated phase body and the mixing of the 2nd synthetic high polymer the time, the flowability of the concentrated phase body in the 2nd synthetic high polymer improves, and becomes to disperse easily.
In addition, with respect to 100 weight portion living beings origin compositions, the addition of alkali metal salt is 0.001～5 weight portion preferably.At this, under the situation of the addition of alkali metal salt less than 0.001 weight portion, the cohesive force of living beings origin composition can not die down, under situation more than 5 weight portions, the viscosity of living beings origin composition descends too many, and the mixing property reduction between the 1st synthetic high polymer, and is not good.
Vegetation matter system or chitin system in addition, when making the concentrated phase body, be not limited to starchiness system, even also can utilize the dispersion of existence promotion in the continuous phase of the 1st synthetic resin of sufficient moisture as mentioned above with the mixing living beings of the 1st synthetic resin.Therefore, be purpose with the dispersiveness that improves living beings origin composition, to append moisture as the living beings of raw material after, put in the kneading device sometimes.
And, when making the concentrated phase body, make compatilizers such as saturated carboxylic acid, unsaturated carboxylic acid or their derivative also mixing together and make the esterification of living beings origin composition sometimes.
As such saturated carboxylic acid, can list succinyl oxide, butanedioic acid, phthalic anhydride, phthalic acid, tetrabydrophthalic anhydride, adipic anhydride etc.As unsaturated carboxylic acid, can list maleic acid, maleic anhydride, nadic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, sorbic acid, acrylic acid etc.
As the derivative of unsaturated carboxylic acid, can use slaine, acid amides, acid imide, ester of above-mentioned unsaturated carboxylic acid etc.
And, as the opportunity that imports these compatilizers, there are following several situations: roughly put into situation in the kneading device simultaneously with living beings origin composition, the 1st synthetic high polymer; Before dropping into kneading device and implement to utilize compatilizer to make the situation of the pre-treatment of living beings origin composition esterification in advance; Before dropping into kneading device, implement to make in advance by unsaturated carboxylic acid and derivative thereof in advance the situation of the pre-treatment of the 1st synthetic high polymer sex change.
When above-mentioned compatilizer acts on living beings origin composition, be replaced into ester group (esterification), show hydrophilic living beings origin composition usually and the low compatibility that shows usually in the interface between the hydrophobic synthetic resin is enhanced by its surperficial alkyl.Thus, improve the compatibility between living beings origin composition and the 1st synthetic high polymer, therefore living beings origin composition can not assembled in the concentrated phase body, also be enhanced with the compatibility between the 2nd synthetic high polymer that cooperates afterwards, thus living beings origin composition is fine and equably high speed dispersion to by in the mixing composite.And the flow behavior of mixing body also improves, and has improved each character of composite.
In the concentrated phase body, as the cooperation ratio of living beings origin composition and the 1st synthetic high polymer, with respect to 100 weight portion living beings origin compositions, the 1st synthetic high polymer is preferably 5～100 weight portions.
During the 1st synthetic high polymer less than 5 weight portions, just can't be by of all adhesional wettings of surface of the 1st synthetic high polymer with the living beings origin composition of miniaturization.So, the 2nd synthetic high polymer is coupled to the concentrated phase body and carries out when mixing, the compatibility of living beings origin composition and the 2nd synthetic high polymer reduces sometimes, has hindered the even dispersion of the living beings origin composition in the composite.
The 1st synthetic high polymer is during more than 100 weight portions, and the component of the 2nd synthetic high polymer of cooperation relatively reduces.So, the diffusion of the living beings origin composition of 2nd synthetic high polymer lower than the relative high viscosity of the 1st synthetic high polymer and space occupancy is slack-off, has hindered the even dispersion of living beings origin composition.
The manufacture method of concentrated phase body
Make the manufacturing installation of concentrated phase body as adding hot milling, for example can list the extruder of vane type batch mixer, closed mixer, single screw rod or twin-screw etc.These manufacturing installations also need to have the dehydration part that moisture that mixing body is comprised dewaters except the general structure that has.
Because mixing body is in the closed state of high temperature, high pressure by the inside of mixing manufacturing installation,, just can play a role as such dehydration part as long as therefore be provided with switching atmospheric air releasing passage freely with the internal communication of this manufacturing installation.
And,,, just can dewater to the moisture that mixing body comprised more efficiently as long as the pressure decompressor that the inner pressure relief that can make manufacturing installation becomes the pressure that forces down than atmosphere can also be set as dehydration part.
Living beings, the 1st synthetic high polymer, suitable compatilizer, alkali metal salt and the moisture that will carry out the pre-treatment of regulation is directly put in the raw material input port of manufacturing installation of such concentrated phase body.And the living beings that need only as raw material are the living beings that derive from starch, also suitably drop into amylase.
Then, mixing zone is set at set point of temperature mixing that professional etiquette fixes time of going forward side by side, forms living beings origin composition and be distributed to state in the 1st synthetic high polymer imperceptibly.
Living beings are with water when mixing like this, and the water of activation enters between the strand of living beings and makes its intermolecular combination loosening.And, to utilize by the mixing mechanical energy of paying, living beings are broken and carry out miniaturization.And the 1st synthetic high polymer (wax) of fusion forms blended liquid phase with water, and is adsorbed on the living beings surface, improves the lipophile of living beings.
Then, as if the atmospheric air releasing passage of opening dehydration part from this state, the moisture that mixing body comprised is released in the atmosphere owing to pressure differential.And, also can make and force the decompressor action and dewater reliably.
At last, the mixing body of the concentrated phase body that takes out from the conveying end of the manufacturing installation of concentrated phase body carries out granulation (granulating) by known prilling granulator.
The particle of the living beings concentrated phase body of the polymer composite of Zhi Zaoing is miniaturization living beings origin composition forms to be coupled at high proportion in the 1st synthetic high polymer like this.And, the moisture that plays a role as the dispersion promoter of disperseing in the 1st synthetic high polymer is reduced make like this to be combined with the concentrated phase body of living beings origin composition at high proportion.Thus, the moisture of being discharged by dehydration part also is a small amount of just enough, can not reduce the productivity ratio of concentrated phase body.
(for the 2nd synthetic high polymer)
For the 2nd synthetic high polymer that is coupled in the concentrated phase body, also take thermoplastic resin or thermosetting resin sometimes, but so long as the material good with the compatibility of the 1st synthetic high polymer, then there is no particular limitation.
But, concentrated phase body and the 2nd synthetic high polymer are carried out mixing when making biomass composite, good dispersed and other each characteristics in order to ensure the living beings origin composition in this composite, the 1st synthetic high polymer and the 2nd synthetic high polymer preferably have the relation of following formula, (wherein being only limited to the situation that is crystalline polymer).
T1≤T2 ...(2)
At this, T1 represents the fusion peak temperature Tpm by dsc measurement of the 1st synthetic high polymer, and T2 represents to be coupled to the fusion peak temperature Tpm of the 2nd synthetic high polymer in the concentrated phase body.At this, so-called fusion peak temperature Tpm is meant the temperature (with reference to JISK7121) by the summit at the fusion peak of dsc measurement.
But, generally not that temperature Tp m with this summit is the symmetric shape at center as the fusion peak by dsc measurement of the synthetic resin of crystalline polymer.But, melting temperature is set to the temperature that the 2nd synthetic high polymer fully fuses, under this design temperature, if concentrated phase body and the 2nd synthetic high polymer are by mixing, before the 2nd synthetic high polymer becomes molten mass from solid, the 1st synthetic high polymer is fusion in advance, becomes molten mass, spreads all over equably in the whole mixing body.
And (T1＜T2) has the little such flow behavior of viscosity under melting temperature to the 1st synthetic high polymer that fusion peak temperature Tpm is lower than the 2nd synthetic high polymer usually.Therefore, at the mixing initial stage, the molten mass of low viscous concentrated phase body is filled in the gap of particle of the 2nd synthetic high polymer of solid in advance, and the effect that therefore also can obtain to make the internal flow resistance of kneading device to reduce contributes to the formability of composite, the lifting of productivity ratio.
And the situation of T1=T2 is meant that the 1st synthetic high polymer comes down to identical synthetic resin with the 2nd synthetic high polymer, can realize by mixing mixing thing compatibility each other good state extremely.Thus, living beings origin composition evenly spreads in the whole composite, and has improved formability, the productivity ratio of composite.
(the manufacture method 1 of composite; The 2nd synthetic high polymer is the situation of thermoplastic resin)
To be coupled to as the 2nd synthetic high polymer of thermoplastic resin in the particle of the concentrated phase body of making by the manufacture method of above-mentioned concentrated phase body, and be undertaken mixing by kneading device together.The kneading device that is adopted can list the extruder etc. of vane type batch mixer, batch mixing roller, sealed batch mixer, single screw rod or the twin-screw of extensive employing.
To carry out appending wax sometimes in the mixing operation as the 2nd synthetic high polymer and the concentrated phase body of thermoplastic resin, making wax phase be contained in the scope of 0.5～30 weight % for the weight occupation rate of the gross weight of finally manufactured composite.Thus, the viscosity of mixing thing reduces, and the burden of kneading device reduces, and improves mixing property, and living beings origin composition evenly and imperceptibly is distributed in the 2nd synthetic high polymer continuous phase.
Under the situation of weight occupation rate less than 0.5 weight % of wax, can't with wax with miniaturization the surface adhesional wetting of living beings origin composition.So, be difficult to the decentralized photo of hydrophilic living beings is diffused in the continuous phase of hydrophobic synthetic resin equably.
On the other hand, under the situation of the use level of wax more than 30 weight %, the mean molecule quantity of the synthetic resin composition of the composite of formation manufacturing reduces, and its engineering properties reduces.
And, from these kneading devices the molten mass of composite is imported to injection molded, extrusion molding, blow molding, in the building mortion of various thermoplastic resins such as expansion-molded, can make following various product: the various products that in the past adopted thermoplastic resin to process, to be reduced into the various products that soil is purpose by landfill, household appliances for example, agricultural aquatic products industry material, the civil construction material, but outdoor leisure treatment product, packaging film, refuse bag, in the desert, the tree planting material that adopt in wasteland etc., fishing line, fishnet, packaging film, amenities such as paper nappy, stationery, container, pallet, foreign material etc.
(the manufacture method 2 of composite; The 2nd synthetic high polymer is the situation of thermosetting resin)
The concentrated phase body that to be made by the manufacture method of above-mentioned concentrated phase body mixes with the 2nd synthetic high polymer as thermosetting resin, puts in the building mortion of the common thermosetting resin that is adopted, and can make biomass composite.
The building mortion that is adopted can list compressing forming machine, injection molding machine, transfer modling forming machine etc. particularly, can make in the past the various products made with thermosetting resin, car parts, electric component, electronic component etc.
Adopting compressing forming machine to make under the situation of composite, the mixture of concentrated phase body and thermosetting resin (the 2nd synthetic high polymer) to be put in the recess (die cavity) of the mould that is set to solidification temperature, pressurization makes its curing.In this case, make the living beings concentrated phase body liquidation of polymer composite by heating, be filled in the gap of the 2nd synthetic high polymer particle.Afterwards, carry out the curing reaction of the 2nd synthetic high polymer, can obtain living beings origin composition and disperse evenly and imperceptibly the biomass composite that forms.
Adopting injection molding machine or transfer modling forming machine to make under the situation of composite, the mixture of concentrated phase body and thermosetting resin (the 2nd synthetic high polymer) is being set at the flowing temperature of the temperature lower than solidification temperature, making the mixture liquidation.Then, the mixture (concentrated phase body+the 2nd synthetic high polymer) of this liquidation is pressed in the mould that is set at solidification temperature, makes mixture solidified.
In addition, for miniaturization, the homogenising of the decentralized photo of realizing living beings origin composition, preferably fully stir the mixture that is in flow regime.
Perhaps, also can be in being mixed into the 2nd synthetic high polymer before, with mixer etc. the particle of concentrated phase body is carried out pulverization process.In this case, pulverized living beings origin composition surface is the face of new formation, therefore obtains easily also to uprise and uniform decentralized photo with the compatibility of thermosetting resin.
Reason is, in this case, is turned to preceding dike by pulverization process by particulate during with formed composite material, and the particle of the concentrated phase that is shaped body makes the surface area that contacts with the air in the external world with prescribed level (the common size such from the big grain of rice to beans) diminish.
This not only guarantees above-mentioned such pulverizing and significantly by the face of the new formation of micronized living beings origin composition, and suppresses the concentrated phase body and generate heat owing to surface oxidation, pays the storage stability of energy long preservation.
In addition, in the manufacturing process of the manufacturing process of above-mentioned concentrated phase body or composite, dropping into average grain diameter sometimes as deodorant is that silica powder below 50 microns or the known biological degradability that drops into the decomposition when promoting landfill disposal are paid agent.
Like this,, adopt common kneading device, can make the decentralized photo of living beings origin composition fine and be distributed to equably in the continuous phase of synthetic resin, can produce biomass composite easily in batches by utilizing the concentrated phase body.

Claims (18)

1. the manufacturing installation of a polymer composite, this polymer composite mixes synthetic high polymer and living beings origin composition, and this manufacturing installation is characterised in that it comprises:
Mixing parts, its mixing thing to the superfluous moisture thing that contains above-mentioned living beings origin composition at least under the melting temperature that is set carries out mixing;
Dehydration part, it is forcing down than the saturated vapor under the above-mentioned melting temperature and above-mentioned mixing thing is being dewatered under the high setting pressure than atmospheric pressure;
Take out parts, it is used to take out the above-mentioned mixing thing that has dewatered.
2. the manufacturing installation of polymer composite according to claim 1 is characterized in that,
Above-mentioned mixing parts comprise:
Cylinder body, the input parts trip side disposed thereon that drops into the superfluous moisture thing of the host of above-mentioned synthetic high polymer and above-mentioned living beings origin composition, above-mentioned taking-up parts are arranged on its downstream,
And screw rod, rotate around axis in the inside of the above-mentioned cylinder body that is set to above-mentioned melting temperature, and above-mentioned mixing thing extruded towards above-mentioned taking-up parts from above-mentioned input parts,
Above-mentioned dehydration part comprises:
Filter, its inside and outside thereof with above-mentioned cylinder body separates, and optionally filters the moisture that is contained in the above-mentioned mixing thing,
Isolated wall, it is used to form gasification space and the isolated atmosphere that makes the moisture gasification of being filtered by above-mentioned filter,
And voltage regulation part, its air pressure with above-mentioned gasification space is set at above-mentioned setting pressure.
3. the manufacturing installation of polymer composite according to claim 2 is characterized in that,
The moisture thing of above-mentioned surplus, aqueous reagent or water are pressed into from the pressing parts in the downstream that is arranged on above-mentioned input parts.
4. the manufacturing installation of polymer composite according to claim 1 is characterized in that,
Above-mentioned mixing parts comprise:
Housing, it is provided with the input parts and the above-mentioned taking-up parts of the superfluous moisture thing of the host that drops into above-mentioned synthetic high polymer and above-mentioned living beings origin composition;
And rotor, it is in the inside rotation that forms enclosure space and be set to the above-mentioned housing of above-mentioned melting temperature, above-mentioned mixing thing is carried out mixing,
Above-mentioned dehydration part has:
Be used for the air pressure of above-mentioned enclosure space is set at the voltage regulation part of above-mentioned setting pressure.
5. the manufacturing installation of polymer composite according to claim 4 is characterized in that, comprising:
Filter, it separates the inside and outside of above-mentioned housing, and optionally filters contained moisture in the above-mentioned mixing thing;
And isolated wall, it forms the gasification space that is communicated with above-mentioned enclosure space via above-mentioned filter, and is provided with above-mentioned voltage regulation part.
6. the manufacture method of a polymer composite, this polymer composite mixes synthetic high polymer and living beings origin composition, and the manufacture method of this polymer composite is characterised in that it comprises:
Mixing operation, the mixing thing to the superfluous moisture thing that contains above-mentioned living beings origin composition at least under the melting temperature of setting carries out mixing;
Dehydration procedure is forcing down than the saturated vapor under the above-mentioned melting temperature and mixing thing is being dewatered under the high setting pressure than atmospheric pressure;
Take out operation, take out the mixing thing that has dewatered.
7. the manufacture method of polymer composite according to claim 6 is characterized in that,
It is living beings that above-mentioned living beings origin composition derives from starchiness, and it comprises and injects that to make this starchiness be the water filling operation of the living beings water that forms superfluous moisture thing.
8. the manufacture method of polymer composite according to claim 6 is characterized in that,
Above-mentioned living beings origin composition forms living beings mechanicalness micronize, comprises that the aggregate that makes above-mentioned living beings origin composition contains immersion and forms the moisture operation of superfluous moisture thing.
9. the manufacture method of polymer composite according to claim 6 is characterized in that,
In above-mentioned mixing operation, the superfluous moisture thing and the compatilizer of above-mentioned living beings origin composition is mixing,
After above-mentioned dehydration procedure, the host of the mixing above-mentioned synthetic high polymer one-step melting of going forward side by side.
10. polymer composite, it is by the resulting polymer composite that is dispersed with living beings origin composition of the described manufacture method of claim 6.
11. a formed products, it forms the described polymer composite that is dispersed with living beings origin composition of claim 10 and obtains.
12. the living beings concentrated phase body of a polymer composite, it is characterized in that, this concentrated phase body is the main composition key element with the 1st synthetic high polymer and living beings origin composition, and it is the raw material of the composite made by the concentration that cooperates the 2nd synthetic high polymer to dilute above-mentioned living beings origin composition.
13. the living beings concentrated phase body of polymer composite according to claim 12 is characterized in that,
Above-mentioned the 1st synthetic high polymer contains wax, and the carbon number of the main chain of the chain hydrocarbon of this wax is contained in 10～100 the scope.
14. the living beings concentrated phase body of polymer composite according to claim 12 is characterized in that,
Above-mentioned the 1st synthetic high polymer is a main component with the olefin-based resin that is synthesized by single site catalysts.
15. the living beings concentrated phase body of polymer composite according to claim 12 is characterized in that,
Above-mentioned living beings origin composition is a main component with amylose, amylopectin or their analyte that derives from starch,
Sneak into starch is carried out amylase or its thermal denaturation thing after enzyme decomposes.
16. the living beings concentrated phase body of polymer composite according to claim 12 is characterized in that it is combined with alkali metal salt.
17. the living beings concentrated phase body of polymer composite according to claim 12 is characterized in that,
Above-mentioned living beings origin composition is by saturated carboxylic acid, unsaturated carboxylic acid or their esterification of derivatives.
18. the manufacture method of a polymer composite is characterized in that, it comprises that the living beings concentrated phase body with the described polymer composite of claim 12 mixes and mixing operation with above-mentioned the 2nd synthetic high polymer.
CN200880014294A 2007-05-01 2008-04-22 Polymer composite material, apparatus for producing the same and method of producing the same Pending CN101678564A (en)

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